Production of cycloalkylaromatics

ABSTRACT

CYCLOALKYLAROMATICS ARE PRODUCED FROM AROMATIC HYDROCARBONS IN THE PRESENCE OF HYDROGEN AND AN AQUEOUS HF-TREATED RUTHENIUM HALIDE-ACTIVE CLAY CATALYST WHICH HAS BEEN PROMOTED WITH AT LEAST ONE COMPOUND OF IRON, COBALT, AND NICKEL. PREFERABLY THE CATALYST HAS NOT BEEN HEATED UNDER CALCINATION CONDITIONS PRIOR TO USE. IN A SPECIFIC EMBODIMENT, BENZENE IS CONVERTED TO CYCLOHEXYLBENZENE WITH GOOD SELECTIVITY OVER AN ACTIVE CLAY IMPREGNATED WITH RUTHENIUM CHLORIDE AND HYDROGEN FLUORIDE AND AT LEAST ONE COMPOUND OF IRON, COBALT, AND NICKEL.

Patented Aug. 13, 1974 3,829,514 PRODUCTION OF CYCLOALKYLAROMATICSErnest A. Zuech, Bartlesville, kla., assignor to Phillips PetroleumCompany No Drawing. Filed Feb. 21, 1973, Ser. No. 334,386 Int. Cl. C07c15/12 U.S. Cl. 260-668 R 7 Claims ABSTRACT OF THE DISCLOSURECycloalkylaromatics are produced from aromatic hydrocarbons in thepresence of hydrogen and an aqueous HF-treated ruthenium halide-activeclay catalyst which has been promoted with at least one compound ofiron, cobalt, and nickel. Preferably the catalyst has not been heatedunder calcination conditions prior to use. In a specific embodiment,benzene is converted to cyclohexylbenzene with good selectivity over anactive clay impregnated with ruthenium chloride and hydrogen fluorideand at least one compound of iron, cobalt, and nickel.

This invention relates to the conversion of aromatic hydrocarbons tocycloalkylaromatics and/ or alkyl-substituted cycloalkylaromatics. Inaccordance with one aspect, the invention relates to an improved processand catalyst for conversion of benzene to cyclohexylbenzene over acatalyst comprising an aqueous HF-treated rutheniumactive clay catalystpromoted with at least one compound of iron, cobalt, and nickel. Inaccordance with a further aspect, this invention relates to an improvedcatalyst for the conversion of aromatics to eycloalkylarmoatics whichcatalyst has been prepared by impregnation of an active clay with anaqueous solution of HF followed by impregnation with an alcoholic oraqueous solution of a ruthenium halide and halide of one of the metalpromoters followed by heating at a temperature below about 380 C. toremove solvent but insuflicient to subject the catalyst composition tocalcination conditions.

Methods are available in the art for the coupling of aro matic nuclei inthe presence of molecular hydrogen to produce an at least partiallyhydrogenated dimer derivative of the aromaticreactant. For example,benzene is converted at elevated temperature to a mixture containingcyclohexylbenzene in the presence of various catalysts.Cyclohexylbenzene is known as a valuable solvent and chemicalintermediate. It can be converted in high yield to phenol andcyclohexanone by autooxidation with subsequent acid treatment. None ofthe prior art methods of producing cyclohexylbenzene have yet beenproven for a stable continuous operation necessary for commercialexploitation. Problems therewith include high catalyst cost, catalyststability and regeneration.

In accordance with the invention there has been discovered a processutilizing an improved ruthenium-clay catalyst which provides not onlyexcellent selectivity for the conversion of aromatics tocycloalkylaromatic hydrocarbons but which is suitable for continuousoperation.

Accordingly, an object of the present invention is to provide animproved process for the conversion of aromatic hydrocarbons tocycoalkylaromatic hydrocarbons.

Another object of the invention is to provide an improved process andcatalyst for the production of cyclohexylbenzene from benzene.

A further object of this invention is to provide an improved rutheniumcatalyst exhibiting excellent selectivity for the conversion of benzeneto cyclohexylbenzene.

Other objects and aspects, as well as the several advantages of theinvention, will be apparent to those skilled in the art upon reading thespecification and the appended claims.

In accordance with the invention, a process is provided for producingcycloalkylaromatics and alkyl-substituted cycloalkylaromatics fromaromatic hydrocarbons by contacting monocyclic aromatic hydrocarbons oralkyl-substituted monocyclic aromatic hydrocarbons with hydrogen in thepresence of an aqueous hydrogen fluoride-treated ruthenium halide-activeclay catalyst promoted with at least one compound of iron, cobalt andnickel.

In accordance with one specific embodiment of the invention, a catalystexhibiting excellent selectivity for the conversion of benzene tocyclohexylbenzene is prepared by impregnating an aqueous HF-treatedactive clay with an alcoholic or aqueous solution of a ruthenium halideand a halide of at least one of iron, cobalt and nickel, followed byheating to remove solvent under non-calcination conditions.

In accordance with another embodiment of the invention, a catalystexhibiting excellent selectivity for the conversion of benzene tocyclohexylbenzene is prepard by impregnating an active clay with aqueoushydrofluoric acid prior to impregnation with an aqueous or alcoholicsolution of ruthenium halide and at least one compound of iron, cobaltand nickel.

In a further embodiment of the invention, benzene is converted tocyclohexylbenzene in good selectivity over an aqueous HF-treatedruthenium chloride-active clay catalyst promoted with at least onecompound of iron, cobalt or nickel and which catalyst has ben preparedby impregnation of the active clay with an alcohol or aqueous solutionof ruthenium chloride and the promoting compound followed by heating toremove solvent at a temperature not in excess of about 380 C. Thecatalyst is preferably used in tablet form although the impregnatedpowder is suitable. As demonstrated by the specific working examplesherein, benzene is converted to cyclohexylbenzene with good selectivityover the inventive catalyst composites.

The feedstocks which are suitable for use in the present invention arearomatic compounds, i.e., monocychc aromatic hydrocarbons andalkyl-substituted monocyclic aromatic hydrocarbons. Some specificexamples of these are benzene, toluene, the xylenes, and the like, andmixtures thereof.

The aromatic conversion according to the invention can be carried out inthe presence of the above-described catalyst at temperatures as low asC. and under hydrogen pressures as low as 100 p.s.i.g. The reactiontemperature can be as high as 250 C., but it is preferred that no higherthan C. be employed. Hydrogen pressures not exceeding 1,000 p.s.i.g. arealso preferred although hydrogen pressures up to about 2,000 p.s.i.g.can be used. Space velocity defined as volume of the liquid feed pervolume of catalyst per hour (LHSV) should be at least 0.5 and not overabout 20. However, it is preferable that the LHSV be at least 2 and notabove about 15.

The present process is effected in the presence of an aqueous HF-treatedclay-supported ruthenium catalyst promoted with at least one compound ofiron, cobalt, and/or nickel. The ruthenium and metal promoters areapplied to the active clay support material preferably as an alcoholicor aqueous solution of a metal halide salt preferably the chloride.

As indicated above, the support materials for the catalyst of theinvention include the montmorillonite clays which preferably have beencompacted as by tableting or extrusion. Good results are obtained whenan aqueous HF-treated support characterized by montmorillonite structureis impregnated with an alcoholic or aqueous solution of the metalhalides, including the promoter metals, followed by heating to removethe solvent. Filtrol Grade 49 clay is an especially good commerciallyavailable montmorillonite clay for forming catalysts of this invention.Commercially available extruded montmorillonite clays such as FiltrolGrades 62 and 71 can also be employed.

In summary, the preferred embodiment of the present invention is aprocess which comprises contacting benzene preferably containing littleif any sulfur at a temperature of 110 to 175 C. at a LHSV of 2 to 15,and under hydrogen pressure of 200 to 1,000 p.s.i.g., with a catalystcomprising an aqueous HF-treated clay supported ruthenium catalystpromoted with at least one compound of iron, cobalt, and/or nickel whichcatalyst has been prepared by impregnating an aqueous HF-treated claywith an alcoholic or aqueous solution of ruthenium halide and a promotermetal halide followed by removal of the solvent by heating undernoncalcination conditions at a temperature below about 380 C.Cyclohexylbenzene is recovered from the reaction mixture.

The above montmorillonite clays suitable for this invention arepreferably employed in a compacted state although finely divided powderscan also be impregnated if desired. The compacted state formontmorillonite clays can be achieved by two general methods which arewell known in the art. First, there is a method whereby essentially dry(chemically bound water can be present) powdered clay in the presence ofa lubricant such as graphite is formed into tablets, pills, pellets, andthe like by conventional means. The second general method involves theuse of a slurry, paste, or dough of the montmorillonite clay admixedwith a volatile liquid, usually water, to form shaped and compactedmontmorillonite pellets, or extruded shapes such as cylinders, tubes andthe like by conventional means. Regardless of which method is employed,for the purposes of this invention the final compacted montmorilloniteclay in the form of a tablet, pellet or the like has a crushing strengthof from 3-15, preferably from 5-10, pounds.

A typical analysis of dry Filtrol Grade 71 clay powder suitable foremployment in the practice of the present invention is as follows: 71.2%SiO 16.5% A1 3.6% Fe O 3.2% MgO, 2.6% CaO, 1.3% S0 1.0% (K O+Na O), and0.6% T10 (analysis on a volatile free basis).

Suitable clays are available commercially as, for example, Filtrol Grade71, Filtrol Grade 62, Filtrol Grade 49, and the like (sold by FiltrolCorporation, Vernon, Calif.). Filtrol Grade 49 and Filtrol Grade 62clays have the following analysis: 74.0% SiO 17.5% A1 0 4.5% MgO, and1.4% Fe O Samples of Filtrol Grade 49 and Filtrol Grade 62 were analyzedby the supplier after heating the Filtrol samples at 1700 F. In thisheat treatment Filtrols 49 and 62 lost, respectively, 17% and 5%volatiles.

It is presently preferred to contact the active clay as the extrudate orpowdered extrudate with aqueous hydrofluoric acid prior to impregnationwith an aqueous or an alcoholic solution of ruthenium halide and thepromoter metal halides. Alternatively, the active clay can be contactedwith an aqueous solution containing hydrofluoric acid, promoter halideand ruthenium halide. If desired, the active clay can be converted totablets before the aqueous HF treatment. Extrudate or powdered extrudatecan be HF treated, impregnated, dried and used as a catalyst or thedried, impregnated powder can be converted to tablets before use.

Following impregnation of the HF-treated active clay with a solution ofthe ruthenium halide and promoter metal halide salts, the solvent can beremoved in vacuo at ambient temperatures, say, about 25 C. Theimpregnated clay can be further dried by heating at temperatures in therange 110-120 C. although temperatures up to 380 C. can be used. Theheating is continued for a period of time and under conditionssufficient to remove substantially all of the solvent but insufficientto calcine the catalyst composition.

The HF-treated ruthenium-active clay catalyst promoted with a compoundof iron, cobalt, and nickel, and mixture thereof, will contain generallyfrom about 0.01 to 2 weight percent, and preferably 0.1 to 1 weightpercent, ruthenium. The amount of metal promoter present in the catalystwill generally be in the range of 0.001 to 3 weight percent, preferably0.05 to 1 weight percent, iron, cobalt, or nickel. The weight ratio ofruthenium to metal promoter (nickel, cobalt or iron) will be in therange 10:1 to 1:15, preferably 120.5 to 1:1. The amount of HF employedwill be in the range of 1 to 15 weight percent, preferably 5 to 10weight percent, based on the weight of active clay.

The present invention is advantageously practiced under substantiallyanhydrous conditions and can be carried out in a batchwise,semi-continuous or continuous operation. However, continuous operationis more suitable for commercial utilization. In a continuous process,the aromatic hydrocarbon hydrogen feed can be passed over the fixed bedcatalyst in an upflow or downfiow manner.

The reaction can be conducted in the presence of or in the substantialabsence of added reaction solvents or diluents. In the modificationwherein added solvent is employed, the solvents which are liquid atreaction temperature and pressure and are inert to the catalyst,reactants and reaction products are suitably employed. Preferredsolvents to be utilized in this modification are saturated hydrocarbonsof from 6-16 carbon atoms, e.g., acyclic alkanes such as hexane, decane,octane, dodecane, and hexadecane, as well as cycloalkanes such ascyclohexane. cyclooctane, cyclododecane, and decahydronaphthalene.

The operability of the present invention is shown by Examples I-VII(corresponding to runs 1-7 in Table I) using Filtrol Grade-49 as thesupport.

SPECIFIC EXAMPLES (A) Catalyst Preparation (Control Run) A 22.0 g.portion of Filtrol Grade 49 in a ml, round bottomed flask was treatedwith a solution of 0.14 g. ruthenium trichloride and 0.22 g. nickel(II)chloride hexahydrate in 40 ml. ethanol. The ethanol was removed atreduced pressure on a rotary evaporator. The residual material wastransferred to a 500 ml. round bottomed flask, and the 100 ml, roundbottomed flask rinsed with two 25 ml. portions of ethanol. These ethanolwashings were combined with the residual particles in the 500 ml. roundbottomed flask and the ethanol was removed under reduced pressure on arotary evaporator. The residue was used as a catalyst.

(B) Cb clohexylbenzene (Control Run) A charge of 30 ml. (23.9 g.) of theabove catalyst (0.25% Ru, 0.25% Ni) was placed in a /z-inch I.D. upflowtube reactor bedded with 30 ml. of 3 mm. glass beads and the catalystwas covered with 4 mm. glass beads. The system was pressure checked,heated to 150 C., pressured to 500 p.s.i.g. H and benzene was pumped inat a rate of ml/hr. with a slight hydrogen flow during a reaction periodof approximately eight hours. The reactor efiluent was collected in areceiver which was changed at approximately one-hour intervals, and thecomposition of each sample was determined by GLC analysis. The GLCanalyses of samples taken during the last four hours of the run wereaveraged and the results showed an 18.2% conversion based on benzenewith a selectivity of 18% to cyclohexane and 67% to cyclohexylbenzene.

EXAMPLE I (A) Catalyst Preparation A 25 g. portion of Filtrol Grade 49was treated with a solution containing 2.5 g. of 50% hydrofluoric acidand 70 ml. of water. The mixture was allowed to stand 15 minutes at roomtemperature, and the water was removed under reduced pressure on arotary evaporator. The residue was treated with a solution of 0.17 g.ruthenium trichloride and 0.25 g. nickel(II) chloride hexahydrate in 50ml. ethanol. The ethanol was removed under reduced pressure on a rotaryevaporator.

(B) Cyclohexylbenzene (Run 1) A charge of 30 ml. (25.35 g.) of the abovecatalyst [0.25 Ru, 0.25% Ni from ethanol on HF-treated Filtrol Grade 49(5 wt. percent HF/Filtrol)] was placed in a /2-inch I.D. upfiow tubereactor bedded with 30 ml. of 3 mm. glass beads and the catalyst wascovered with 4 mm. glass beads. The reaction was carried out in the samemanner as the control run for a period of approximately 8 hours. The GLCanalyses of samples taken during the last 3% hours of the run wereaveraged and the results showed 13% conversion based on benzene with aselectivity of 13% to cyclohexane and 73% to cyclohexylbenzene.

EXAMPLE II (A) Catalyst Preparation The catalyst was prepared asdescribed in Example I except that an aqueous rather than an ethanolicsolution of ruthenium trichloride and nickel(II) chloride hexahydratewas used.

(B) Cyclohexylbenzene (Run 2) This run was carried out in the samereactor and under approximately the same conditions as the control runfor a period of about 8 hours. A 30 ml. (22.6 g.) portion of the abovecatalyst [0.25% Ru, 0.25% Ni from water on HF-treated Filtrol Grade 49(5 wt. percent I-IF/FiltroD] was used in this run and also in Run 3 ofExample HI. The GLC analyses of samples taken during the last 4 /3 hoursof the run were averaged and the results showed 13% conversion based onbenzene with a selectivity of 15% to cyclohexane and 74% tocyclohexylbenzene.

EXAMPLE HI (RUN 3) The catalyst bed of Example II was used in this runand other parameters remained the same except the henzene was pumped inat 180 ml./hr. rather than 120 ml./hr. The GLC analyses of samples takenduring the last five hours of the run were averaged and the resultsshowed conversion based on benzene with a selectivity of 16% tocyclohexane and 75% to cyclohexylbenzene.

EXAMPLE IV (A) Catalyst Preparation A solution was prepared whichcontained 0.20 g. ruthenium trichloride, 0.30 g. nickel(II) chloridehexahydrate, 50 ml. of water, and 3.0 g. of 50% hydrofluoric acid. A 30g. sample of Filtrol Grade 49 was treated with the above solution andthe water was removed at reduced pressure on a rotary evaporator.

(B) Cyclohexylbenzene (Run 4) This run was carried out using the abovecatalyst [0.25 Ru, 0.25% Ni from water on HF-treated Filtrol Grade 49 (5wt. percent HF/Filtrol)] for a period of about 7 hours. The GLC analysesof samples taken during the last 2% hours of the run showed 10%conversion based on benzene with a selectivity of to cyclohexane and 73%to cyclohexylbenzene.

EXAMPLE V (A) Catalyst Preparation A 30 g. sample of Filtrol Grade 49was allowed to stand for 30 minutes in a mixture of 40 ml. water and 6.0g. of 50% hydrofluoric acid. The water was removed under reducedpressure on a rotary evaporator. The residue was treated with a solutionof 0.20 g. ruthenium chloride and 0.30 g. nickel(II) chloridehexahydrate in 40 ml. ethanol. The ethanol was removed under reducedpressure on a rotary evaporator.

6 (B) Cyclohexylbenzene (Run 5) This run was carried out using the abovecatalyst [0.25 Ru, 0.25 Ni from ethanol on HF-treated Filtrol Grade 49(10 wt. percent HF/Filtrol)] for a period of about 8 hours. The samereactor and approximately the same reaction conditions were used asemployed in the control run. The GLC analyses of samples taken duringthe last five hours of the run showed 16% conversion based on benzenewith a selectivity of 15 to cyclohexane and 70% to cyclohexylbenzene.

EXAMPLE VI (A) Catalyst Preparation A 30 g. sample of Filtrol Grade 49was contacted with a mixture of 70 ml. water and 3.0 g. of 50%hydrofluoric acid for a period of 15 minutes. The water was removedunder reduced pressure on a rotary evaporator. The residual material wastreated with 0.121 g. ruthenium trichloride and 0.181 g. nickel(II)chloride hexahydrate in 50 ml. ethanol. The ethanol was removed underreduced pressure on a rotary evaporator.

(B) Cyclohexylbenzene (Run 6) A charge of 30 ml. (24.6 g.) of the abovecatalyst [0.15% Ru, 0.15% Ni from ethanol on HF-treated Filtrol Grade 49(5 wt. percent HF/Filtrol)] was placed in a tube reactor bedded with 30ml. of 3 mm. glass beads. This run was carried out for a period of about8 hours under approximately the same conditions cited in the controlrun. The GLC analyses of samples taken during the last five hours of therun were averaged and showed 10% conversion based on benzene with aselectivity of 16% to cyclohexane and 74% to cyclohexylbenzene.

EXAMPLE VII (RUN 7) This run was carried out for 8 hours over thecatalyst bed of Example VI but at C. rather than C. The GLC analyses ofsamples taken during the last six hours of the run were averaged andshowed 8% conversion based on benzene with 17% selectivity tocyclohexane and 76% to cyclohexylbenzene.

EXAMPLE VIII (A) Catalyst Preparation A 60 g. portion of Filtrol Grade49 was treated with a solution containing 24 g. of 50% hydrofluoric acidand 75 ml. water. The mixture was allowed to stand 1.5 hours, and thewater was removed under reduced pressure on a rotary evaporator. Theresidue was treated with a solution of 0.17 g. ruthenium trichloride and0.25 g. nickel (II) chloride hexahydrate in 50 ml. ethanol. The ethanolwas removed under reduced pressure on a rotary evaporator.

(B) Cyclohexylbenzene (Control Run) A charge of 30 ml. (25.5 g.) of theabove catalyst [0.25 Ru, 0.25% Ni from ethanol on HF-treated Filtrol 49(20 wt. percent HF/Filtrol)] was placed in a /z-inch I.D. upfiow tubereactor bedded with 30 ml. of 3 mm. glass beads and the catalyst wascovered with 4 mm. glass beads. The reaction was carried out in a mannercomparable to the control run of Table I for a period of 8 hours. TheGLC analyses indicated poorer selectivity to cyclohexylbenzene of thissystem (cyclohexylbenzene/ cyclohexane ratio was 0.7) relative to runs1-7 of Table I.

EXAMPLE IX (A) Catalyst Preparation A 30 g. sample of Filtrol Grade 49was contacted for 30 minutes with a mixture of 40 ml. water and 6 g. ofv ethanol. The ethanol was removed under reduced pressure on a rotaryevaporator.

(B) Cyclohexylbenzene (Control Run) This run was carried out for aperiod of 8 hours using the above catalyst [0.25% Ru, 0.5% Ni fromethanol on HF-treated Filtrol Grade 49 (10 wt. percent HF/ Filtrol)].This run was carried out in a manner comparable to the above controlrun. The GLC analyses of samples taken during the last five hours of therun were averaged and showed 14% conversion based on benzene with 20%selectivity to cyclohexane and 68% to cyclohexylbenzene.

It will be observed from this example that as the amount of metalpromoter (Ni) is increased to a Ru/Ni ratio of 1:2 that selectivitydecreases (cyclohexylbenzene/cyclohexane ratio was 3.35) in comparisonwith Runs 1-7 in Table I where the ratio of Ru/ Ni was 1:1.

EXAMPLE X (A) Catalyst Preparation A 45 ml. sample of Filtrol Grade 49Was treated with a 3:1 stream of heliumzanhydrons HF (HF 40 ml./ min.)for a period of 30 minutes. The HF-treated Filtrol Grade 49 was thencontacted with 0.17 g. ruthenium trichloride and 0.25 g. nickel(-II)chloride hexahydrate in 40 ml. ethanol. The ethanol was removed underreduced pressure on a rotary evaporator.

(B) Cyclohexylbenzene (Control Run) A the catalyst is treated withanhydrous HF (note cyclohexylbenzene/cyclohexane ratios in Runs 1-7 inTable I).

cycloalkylaromatics such as dicyclohexylbenzenes and trifluoride,antimony pentafluoride, and the like. Alterna tively, heterogenouscatalysts such as active clays, zeolites, supported phosphoric acid,fluorided alumina, and the like can also be used.

I claim:

1. A process for producing cycloalkylaromatics and alkyl-substitutedcycloalkylaromatics by contacting a monocyclic aromatic hydrocarbon oralkyl-substituted monocyclic aromatic hydrocarbon with hydrogen in thepresence of an aqueous HF-treated ruthenium-active clay atalystcomprising 0 O1 to about 2 weight percent ruthenium promoted with from0.001 to about 3 weight percent of at least one compound of iron, cobaltand nickel in a weight ratio of the ruthenium to promoter metal in therange 10:1 to 1:15, under conditions sufficient to substantially convertsaid monocyclic aromatic hydrocarbons to cycloalkylaromatics andalkyl-substituted cycloalkylaromatic hydrocarbons.

2. A process according to claim 1 wherein benzene is converted tocyclohexylbenzene by contacting benzene and hydrogen with a rutheniumchloride-montmorillonite active clay catalyst promoted with a halide ofiron, cobalt and nickel or mixtures thereof.

3. A process according to claim 1 wherein said contacting is eifected ata temperature of from about 100 C. to about 250 C. and a hydrogenpressure of from about 100 p.s.i.g. to about 2,000 p.s.i.g. and theamount of HF based on active clay is in the range of 1 to 15 weightpercent.

4. A process according to claim 1 wherein an aqueous HF-treated activeclay is impregnated with an aqueous or alcoholic solution of rutheniumhalide and a halide of at least one of said metal promoters and heatedunder noncalcination ocnditions for a period of time sufficient toremove the solvent.

5. A process according to claim 3 wherein said con- TABLEI.-CYCLOHEXYLBENZENE FROM BENZENE/Hz OVER HIT-TREATED FILTROL 49CATALYSTS Cata- Products, weight percent Seleclyst tivity, prepa- CyBz/CyBz Run N o. Metals on Fitrol 49 ration ClHlZ CtHu Unknown MeCpBz lCyBz 1 Heavies 1 CeHiz percent (a) 3. 2 81. 8 0. 1 12. 2 2. 6 3. 7 67(b) 2. 0 85. 1 0. 1 10. 9 1. 9 5. 6 73 (c) 2. 1 86. 1 0. 15 10. 3 1. 34. 9 74 (c) 1. 8 89. 1 0. 1 8. 2 0. 8 4. 6 75 (d) 1. 8 0. 1 8. 7 1. 3 4.8 73 (8) 2. 8 0. 3 12. 9 2. 5 4. 6 70 (b) 1. 7 0. 1 7. 9 0. 9 4. 65 74(b) 1. 4 0. 1 6. 4 0. 5 4. 76

1 MeCpBz and CyBz represent, respectively, methylcyclopentylhenzene andcyclohexylbenzene. 1 Heavies were estimated by determining the residueremaining after distillation, and normalization of the GLC data.

= LHSV=6. The LHSV is 4 in the other runs.

Nora: (a) Filtrol 49 was not treated with HF; Ru and Ni were added fromethanol solution as Buck and NiClg; (b) 5 weight percent HF based onFiltrol 49 was added to Filtrol 49 from water solution; Ru and Ni wereadded from ethanol solution as RuClr and NiClg; (0) Same as (b) exceptRu and Ni were added from water solution as RuCla and Nick; ((1) A watersolution of RuCh/NiCh/HF was contacted with Filtrol 49 (5 wt. percent HFbased on Filtrol 49); (0) Same as (b) except 10 weight percent HF basedon Filtrol 49 was added to Filtrol 49 from water solution.

The cyclohexylbenzene/cyclohexane ratios of runs 17 tacting is effectedwith a ruthenium trichloride-active clay in Table I indicate the greaterselectivity to cyclohexylbenzene of the inventive runs employing aqueousHF- treated catalytic systems as opposed to the untreated catalystsystem of the control run.

The heavies produced in the present inventive cyclohexylbenzene processcan be equilibrated with benzene in the presence of a Lewis acid such asaluminum chloride to increase the yield of the desiredcyclohexylbenzene. The major by-product components weight percent ofcatalyst at reaction conditions of from about C. to about C. andhydrogen pressure in the range of about 200 to about 1,000 p.s.i.g.

6. A process according to claim 1 wherein cyclohexylbenzene is producedby contacting benzene with hydrogen at a temperature in the range110-175" C. under liquid phase conditions.

7. A process according to claim 6 wherein the liquid phase of benzeneand hydrogen is passed through a bed the heavies) produced in theinventive process are poly- 75 of Filtrol Grade 49 active clay catalystthat has been treated with 1 to 15 weight percent aqueous HF andpromoted with ruthenium and nickel at a liquid hourly space velocity(LHSV) in the range of 2 to 15 and a hydrogen pressure of 200 to 1,000p.s.i.g.

References Cited UNITED STATES PATENTS Hzensel 260-68365 Logemann260-667 Louver 260-671 R 1 Louver et a1 260668 F CURTIS R. DAVIS,

10 Slaugh 260688 F Hartog 260-667 Slaugh et a1 260-668 R Arkell et a1.260-668 R Saggitt et a1 260668 R Crone et a1 260668 R Primary ExaminerUS. Cl. X.R.

